Competing Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3

Jan 17, 2018 - NMR spectra after the photolysis of 1 under p-H2 in toluene-d8 at 220 K: (a) 31P{1H} NMR spectrum showing the formation of 2 and free P...
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Article Cite This: Organometallics XXXX, XXX, XXX−XXX

Competing Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3 Barbara Procacci,†,‡ Simon B. Duckett,*,†,‡ Michael W. George,*,§,∥ Magnus W. D. Hanson-Heine,§ Raphael Horvath,§ Robin N. Perutz,*,† Xue-Zhong Sun,§ Khuong Q. Vuong,§ and Janet A. Welch† †

Department of Chemistry, University of York, York YO10 5DD, U.K. Centre for Hyperpolarisation in Magnetic Resonance, Department of Chemistry, York Science Park, University of York, York YO10 5NY, U.K. § School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K. ∥ Department of Chemical and Environmental Engineering, The University of Nottingham Ningbo China, 199 Taikang East Road, Ningbo 315100, People’s Republic of China ‡

S Supporting Information *

ABSTRACT: The photochemistry of Ru(H)2(CO)(PPh3)3 (1) has been reinvestigated employing laser and conventional light sources in conjunction with NMR spectroscopy and IR spectroscopy. The sensitivity of NMR experiments was enhanced by use of p-H2-induced polarization (PHIP), and a series of unexpected reactions were observed. The photoinduced reductive elimination of H2 was demonstrated (a) via NMR spectroscopy by the observation of hyperpolarized 1 on pulsed laser photolysis in the presence of p-H2 and (b) via nanosecond time-resolved infrared (TRIR) spectroscopy studies of the transient [Ru(CO)(PPh3)3]. Elimination of H2 competes with photoinduced loss of PPh3, as demonstrated by formation of dihydrogen, triphenylarsine, and pyridine substitution products which are detected by NMR spectroscopy. The corresponding coordinatively unsaturated 16electron intermediate [Ru(H)2(CO)(PPh3)2] exists in two isomeric forms according to TRIR spectroscopy that react with H2 and with pyridine on a nanosecond time scale. These two pathways, reductive elimination of H2 and PPh3 loss, are shown to occur with approximately equal quantum yields upon 355 nm irradiation. Low-temperature photolysis in the presence of H2 reveals the formation of the dihydrogen complex Ru(H)2(η2-H2)(CO)(PPh3)2, which is detected by NMR and IR spectroscopy. This complex reacts further within seconds at room temperature, and its behavior provides a rationale to explain the PHIP results. Furthermore, photolysis in the presence of AsPh3 and H2 generates Ru(H)2(AsPh3)(CO)(PPh3)2. Two isomers of Ru(H)2(CO)(PPh3)2(pyridine) are formed according to NMR spectroscopy on initial photolysis of 1 in the presence of pyridine under H2. Two further isomers are formed as minor products; the configuration of each isomer was identified by NMR spectroscopy. Laser pump-NMR probe spectroscopy was used to observe coherent oscillations in the magnetization of one of the isomers of the pyridine complex; the oscillation frequency corresponds to the difference in chemical shift between the hydride resonances. Pyridine substitution products were also detected by TRIR spectroscopy.

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INTRODUCTION Photochemical methods offer low-temperature routes to synthesis, excellent routes to study reaction mechanisms, and great opportunities for catalysis. Indeed, there has been a great resurgence of interest in photocatalysis.1−3 Metal hydrides play a major part in the photochemistry of organometallics and coordination complexes, and we have recently reviewed their behavior systematically.4 One of the earliest metal hydrides to be studied photochemically was Ru(H)2(CO)(PPh3)3 (1) (Scheme 1), a compound of great interest for its catalytic properties both under illumination and by thermal means.5−13 The original studies of its photochemistry demonstrated loss of H2, but not CO, on irradiation in benzene. Selectivity for loss of H2 over loss of CO is now recognized for several metal carbonyl dihydrides.14 When 1 was photolyzed in benzene solution under a CO atmosphere, Ru(CO)3(PPh3)2 was formed, leaving the sequence in which H2 and PPh3 had been dissociated and CO coordinated uncertain.5 In 1997, we © XXXX American Chemical Society

identified 1 as an excellent target for investigating the photodissociation of H2 by time-resolved UV/vis and timeresolved IR spectroscopy.15 We observed a transient by both techniques that was assigned to [Ru(CO)(PPh3)3] and measured its rate of reaction with H2 ((8.4 ± 0.4) × 107 dm3 mol−1 cm−1 at room temperature). It was of particular importance that the transient exhibited a 95 cm−1 shift to low frequency in its CO-stretching band, providing proof of H2 loss. Moreover, ultrafast spectroscopy demonstrated that it was formed within the response time of the instrument of 6 ps. The only other transient observed by IR spectroscopy had a significant rise time, suggesting that it was a secondary product. Thus, we concluded that there was ultrafast and concerted photochemical reductive elimination of H2 from Ru(H)2(CO)(PPh3)3. As we now show, this study failed to find evidence for Received: November 2, 2017

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DOI: 10.1021/acs.organomet.7b00802 Organometallics XXXX, XXX, XXX−XXX

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were conducted at temperatures ranging from 220 to 300 K. The infrared studies include time-resolved IR spectroscopy at room temperature on time scales from nanoseconds to microseconds and FTIR methods at ca. 220 K. They reveal that photodissociation of PPh3 occurs in addition to reductive elimination of H2, leading to substitution products. We show that it is the interplay of these two pathways that limits the use of PHIP methods when they are applied to 1.

Scheme 1. Structure of 1 and Spectroscopic Features

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RESULTS Characterization of Ru(H)2(CO)(PPh3)3 (1) and Detection of Hyperpolarized 1. Complex 1 (Scheme 1) has been characterized previously,15,34 but a summary of its main spectroscopic features is provided in Scheme 1 and a 1H NMR spectrum of the key hydride region is illustrated in Figure 1a; a 31P{1H} NMR spectrum is shown in the Supporting Information.

a further process because of the limitations of the methodology and the techniques available to us at the time: neither the transient absorption nor the TRIR experiments probed the time scale of 0.5−500 ns, and our steady-state NMR experiments were conducted at room temperature and not at low temperature. The advent of in situ photochemistry at low temperature with NMR detection16−25 offered a new method of probing reaction mechanisms. In the case of a ruthenium complex related to 1 in which one phosphine has been replaced by an Nheterocyclic carbene, Ru(H)2(IEt2Me2)(PPh3)2(CO) (IEt2Me2 = 1,3-bis(ethyl)-4,5-dimethylimidazol-2-ylidene), we showed that the products are actually consistent with two competing pathways: reductive elimination of H2 and dissociation of PPh3.26 Loss of PPh3 was revealed by the formation of a cyclometalation product in the absence of other substrates and Ru(H)2(IEt2Me2)(PPh3)(CO)(L) (L = pyridine, η2-H2) in the presence of H2 or pyridine. The combination of this photochemical technique with p-hydrogen-induced polarization (PHIP) showed weakly enhanced NMR resonances for the precursor and stronger enhancement for two of its isomers. This effect could be understood by photoinduced reductive elimination of H2 followed by oxidative addition of p-H2. Photochemical loss of phosphine competing with loss of H2 was also observed for Ru(H)2(PMe3)4.27 The time scales available and the sensitivity of TRIR spectroscopy have improved greatly since our 1997 study, and there are no longer any gaps in the nanosecond time domain.28−31 Recently, we returned to the photochemistry of 1 and observed some unexpected features in its reactivity toward pH2. We found that we could observe PHIP-enhanced hydride resonances if we used a pulsed laser for excitation (at 355 nm) synchronized to the NMR spectrometer under a pressure of pH2.32 Under these very dilute conditions with single laser shots, there was negligible photodecomposition. Notably, the observed signal enhancement decayed on a millisecond time scale and was only observed with synchronization. This behavior was very different from that of related ruthenium complexes. A paper published in 2017 has repeated these measurements with 308 nm irradiation and a hydrogen pressure of 1 atm. The results are similar, but some photodecomposition has been reported.33 In this paper, we report a series of studies of the photochemistry of 1 by NMR and IR methods; the NMR studies were performed using three types of experiments: (a) broad-band (λ >290 nm) ex situ irradiation, (b) continuous wave (cw) laser (λ 325 nm) in situ irradiation (NMR operating frequency 400 MHz), and (c) pulsed laser (λ 355 nm) in situ irradiation (NMR operating frequency 600 MHz). The studies

Figure 1. Hydride region of two 1H NMR spectra of 1 in C6D6 after (a) 128 scans probing a concentrated solution of 1 and (b) 1 scan of an optically dilute solution after laser-induced incorporation of p-H2 yielding hyperpolarized hydride peaks (τ = 150 μs).

When an optically dilute solution of 1 is irradiated with a single shot of the pulsed laser (355 nm) in the presence of p-H2 (3 bar) and monitored through the response from a single, synchronized rf pulse that takes place up to 5 ms after laser irradiation, enhanced hydride signals at δ −6.47 and −8.30 are observed (Figure 1b). In this spectrum, JHH corresponds to the peak separation of the antiphase features, while the other splittings arise from coupling to 31P nuclei32 (the corresponding 1 H{31P} spectrum is shown in the Supporting Information). Similar hyperpolarization is observed on irradiation at 220 K. This result demonstrates that p-H2 has been incorporated into 1. Formation of hyperpolarized 1 can be understood by reductive elimination of H2 upon 355 nm irradiation yielding [Ru(CO)(PPh3)3], which recombines with p-H2 by oxidative addition. The readdition of H2 to [Ru(CO)(PPh3)3] is known to be fast under these conditions (the time constant for recombination under 3 atm of H2 is 1.4 μs), precluding the detection of any transient species. NMR Studies of the Photochemistry of 1. Formation of Ru(H)2(η2-H2)(CO)(PPh3)2 (2). In contrast to the measurements described above, the steady-state photolysis of an optically dilute solution of 1 under a p-H2 atmosphere at 295 K in benzene-d6 or toluene-d8 undertaken either ex situ (λ >290 nm) or in situ with a laser (λ 325 nm, cw) resulted in no change in the observed NMR spectra of these solutions and PHIP was no longer observed in the hydride resonances of 1. Notably, a very intense peak for o-H2 was visible before irradiation was initiated, indicating consumption of p-H2 via a thermal route. B

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Organometallics When the in situ irradiation process with p-H2 was repeated at 223 K (toluene-d8), there was still no PHIP enhancement of 1 upon photolysis (2 min, λ 325 nm). However, a new broad resonance (fwhm ca. 63 Hz at 400 MHz) was observed at δ −5.82 in the 1H NMR spectrum along with new signals in the aromatic region indicating productive photochemistry and the formation of the new species 2 (Figure 2a).

Scheme 2. Competing Photochemistry of 1 under H2 Atmosphere

in detail by Crabtree.36 Furthermore, the disappearance of 2 upon warming is consistent with the well-known lability of dihydrogen as a two-electron-donor ligand.37 Complex 2 is an analogue of Ru(H)2(η2-H2)(PPh3)3 that is formed from Ru(H)2(PPh3)4 thermally and is also closely related to [Ru(IPr) 2 (CO)(η 2 -H 2 )H]BArF 4 (IPr = 1,3-bis(2,6diisopropylphenyl)imidazol-2-ylidene).38−40 Comparisons may also be made to Ru and Ir complexes studied with partial deuteration.41,42 In order to confirm the presence of a dihydrogen ligand in 2, data for T1 were recorded at 400 MHz between 212 and 242 K for the resonance at δ −5.82. The value of T1(min) for 2 proved to be 35 ± 2 ms at ca. 225 K, whereas the corresponding value of T1 for the hydride resonances of 1 was much longer (390 ms at 298 K). This is consistent with a dihydrogen arrangement, as such ligands are known to relax much more quickly than their hydride analogues.37,43 Further analysis of the T1 values is given in the Supporting Information. We have already shown that PHIP was observed for the hydride resonances of 1 when a solution of 1 (C6D6) under pH2 (∼4 bar) was irradiated at 298 K with a pulsed laser (355 nm) synchronized to the spectrometer.32 However, if this sample was irradiated with multiple laser shots (4 sets of 32 laser shots,10 Hz repetition rate, 1 NMR scan), 2 was detected, although its signal disappeared after the first NMR scan due to its low stability. As complex 2 disappeared, the signals for 1 and a new hydride resonance started to grow in a thermal reaction. This new product signal appears at δ −6.34, as a triplet with J = 23 Hz, that connects to a single 31P{1H} resonance at δ 57.1 and simplifies into a singlet upon 31P decoupling; it is assigned to the known Ru(H)2(PPh3)2(CO)2.44,45 Additional evidence for formation of 2 was obtained by photolysis of 1 under a D2 atmosphere at 298 K using either a pulsed or continuous laser. Depletion of the hydride signal for 1 occurred during photolysis along with the appearance of peaks for H2 (δ 4.46 in C6D6, s) and HD (δ 4.41 in C6D6, t, JHD = 43 Hz). There was also evidence of partial deuteration of 1 through broadening of the hydride resonances. Direct reductive elimination accounts for the formation of H2. HD is logically formed through loss of PPh3 and initial η2 coordination of D2 to form the deuterium analogue of 2 followed by intramolecular exchange with the hydride ligands to yield Ru(H)(D)(HD)(CO)(PPh3)2 and ultimately HD. Complex 1-d2 was generated by a sequence of three cycles of photolysis of 1 under D2 (3 atm), followed by replacement of the atmosphere by fresh D2 and further photolysis. At this stage, no HD or hydride resonances for 1 could be detected. Photoreaction (325 nm) of the preformed 1-d2 with H2 at 223 K was then followed by 1H NMR and, as expected, the hydride signals of both 1 and 2

Figure 2. NMR spectra after the photolysis of 1 under p-H2 in toluene-d8 at 220 K: (a) 31P{1H} NMR spectrum showing the formation of 2 and free PPh3; (b) hydride region of the 1H spectrum displaying signals for 1 and a broad resonance for 2.

The 31P{1H} NMR spectrum now displayed two new singlets at δ −6.0 and 59.4 in addition to the resonances of 1. The new 31 1 P{ H} peak resonating at δ −6.0 was identified as free PPh3, and an experiment with inverse-gated decoupling (quantitative phosphorus) showed that the integration ratio of the unknown peak to the free PPh3 is 2:1, suggesting that 2 contains two equivalent PPh3 ligands (Figure 2b). Further cooling to 193 K resulted in no change in these NMR features; however, warming to 295 K led to the disappearance of these signals and re-formation of 1. Complex 2 could also be generated at low temperatures with pulsed laser irradiation (λ 355 nm, 48 laser shots, 10 Hz repetition rate). On the basis of these results, we assign 2 as the dihydrogen complex Ru(H)2(η2-H2)(CO)(PPh3)2 formed by photochemically induced PPh3 loss from 1 and coordination of H2 (Scheme 2). Upon cooling to 193 K the associated NMR spectra of 2 show minimal change. Moreover, when a 1H{31P} NMR spectrum was recorded at 220 K using a broad-band decoupling sequence, the peak for 2 remained unaltered whereas the resonances for 1 simplified to doublets retaining only a JHH value of 6 Hz between the two hydrides. These observations are fully consistent with rapid exchange between hydride and dihydrogen ligands in conjunction with quick relaxation and the averaging of hydride−phosphorus couplings to a small and hence invisible value. The exchange is likely to occur by the σ-CAM mechanism,35 as has been shown C

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spectrum and simplify into antiphase doublets upon 31P decoupling. The triplet splitting is due to coupling to two equivalent 31P nuclei that lie cis to the hydrides (δ −6.28, JPH = 30 Hz; δ −9.46, JPH = 26 Hz). We therefore assign 3 to Ru(H)2(AsPh3)(CO)(PPh3)2, formed by PPh3 loss and AsPh3 coordination, with the geometry shown in Scheme 3. Free PPh3

were seen. Although this sample should contain partially deuterated 2, no JHD splitting was observed, even at 193 K. The lack of a visible HD splitting is consistent with rapid exchange between the hydride and dihydrogen ligands.37 Although the two hydride ligand signals of 1 are distinct at room temperature, heteronuclear NOESY experiments have previously demonstrated that 1 undergoes intramolecular ligand exchange at 335 K where the two hydrides exchange with each other as well as with the inequivalent phosphines.46 The exchange was postulated to occur via a trigonal twist mechanism, but alternative mechanisms involving dihydrogen isomers are also possible (see Discussion). We undertook a series of 1D EXSY experiments to probe for the thermal exchange of 1 with free H2 or free PPh3. The two hydride peaks and free hydrogen peak were monitored at mixing times between 50 and 800 ms in C6D6 solution. As expected, slow intramolecular exchange between the two hydride resonances was observed at room temperature and faster exchange at 333 K as previously reported,46 but no exchange with free H2 was detected up to 333 K, demonstrating that no thermal H2 elimination occurs on the EXSY time scale of ca. 1 s (see the Supporting Information). In similar experiments, exchange between free PPh3 and the phosphine ligands was monitored at 333 K (see the Supporting Information). Once more, no intermolecular exchange was observed, in agreement with the literature.46 The photoreactions of 1 under H2 provide evidence for H2 reductive elimination and readdition through PHIP of 1; evidence for competing PPh3 dissociation is seen via the observation of 2 and the formation of HD on photolysis under D2. Formation of Ru(H)2(AsPh3)(CO)(PPh3)2 (3). In order to further probe the phosphine loss pathway, a sample of 1 (C6D6) was prepared under p-H2 (∼4 bar) in the presence of a 10-fold excess of AsPh3. A 1H{31P} NMR spectrum measured prior to photolysis revealed slight conversion of 1 into the new species 3 with two very weak hydride resonances at δ −6.28 and −9.46 (JHH = 6 Hz) and a new singlet in the 31P{1H} spectrum at δ 58. When the sample was exposed to a single laser shot at 295 K, the hydride resonances of both 1 and 3 became PHIP-enhanced (Figure 3). The intensities of the new product peaks were also found to increase on irradiation with more laser shots. These peaks are split into triplets of antiphase doublets, in an overall 1:1 intensity ratio, in the 1H NMR

Scheme 3. Photochemistry of 1 in the Presence of Excess AsPh3 and p-H2

was detected in the 31P{1H} spectrum, as expected. Some thermal loss of PPh3 occurs, as is evident from the presence of a small amount of 3 before irradiation. Additionally, these observations also confirm that photolysis causes PPh3 loss along with H2 reductive elimination. Complex 3 is relatively stable and can still be detected at room temperature after the p-H2 response has decayed. Formation of Ru(H)2(CO)(PPh3)2(pyridine). An analogous reaction was then undertaken where AsPh3 was replaced with pyridine. The thermal reaction of 1 with pyridine under p-H2 (4 bar) at 298 K was first monitored in toluene-d8 with added pyridine (10 μL). No reaction was observed by conventional NMR spectroscopy at 295 K; notably, the presence of pyridine suppressed the conversion of p-H2 to o-H2 that had been observed in the absence of pyridine. However, when this process was repeated using the high-sensitivity Only Pphydrogen SpectroscopY (OPSY)47 approach, two weak hydride resonances were observed that we assign to the complex Ru(H)2(CO)(PPh3)2(pyridine) (4-CN). (We label the isomers of 4 according to the ligands that lie trans to the mutually cis hydride ligands. Thus, 4-CN indicates that the cis hydride ligands are trans to C and N; see below.) Conversion to this product improved on increasing the temperature to 345 K, confirming a thermal route to its formation. The same product could be generated more efficiently by photochemical reaction in neat pyridine; after 3 h irradiation (λ >290 nm, 295 K), 80% of the starting material 1 was converted to 4-CN along with some minor byproducts (see later). The hydride region of the 1H NMR spectrum, measured without hyperpolarization, shows two major resonances for 4CN as a triplet of doublets at δ −4.59 (JPH = 27 Hz, JHH = 6.5 Hz) and δ −14.32 (JPH = 23 Hz, JHH = 6.5 Hz) in a 1:1 ratio. These signals simplify into doublets when 31P is decoupled. The corresponding 31P{1H} NMR spectrum displayed a singlet at δ 65.4 for the main product. On the basis of these results we assign 4-CN to Ru(H)2(CO)(PPh3)2(NC5H5), an analogue of 3, with mutually trans PPh3 groups formed by photochemical PPh3 loss and reaction with pyridine. The hydride resonance at δ −14.32 displayed a chemical shift characteristic of a hydride trans to nitrogen,48 while the remaining hydride is assigned as trans to CO; free PPh3 was also detected in the 31P{1H} spectrum. Attempts to isolate 4-CN were unsuccessful due to the lability of the pyridine ligand; when the sample was pumped to dryness and redissolved in benzene, 1 was regenerated almost quantitatively (see the Supporting Information). When this reaction was repeated with a 10-fold excess of C5D5N in benzene, the same product distribution was observed.

Figure 3. Hydride region of a series of 1H NMR spectra of a solution of 1 in C6D6 in the presence of a 10-fold excess of AsPh3 under p-H2 at room temperature showing hyperpolarized signals for 1 and 3 after (a) 1 laser shot, (b) 2 laser shots, and (c) 4 laser shots. D

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after a single laser shot with a single NMR scan.32 When the laser was allowed to fire two shots consecutively (10 Hz repetition rate), PHIP-enhanced resonances of 4-CN also became visible after one NMR scan, observed as triplets of antiphase doublets in the 1H NMR spectrum. A weakly hyperpolarized resonance at δ −4.82 with a shape that indicates a product with an AA′XX′ spin system was also observed (Figure 4b). We assign it to 4-PP, an isomer of 4-CN with a square-planar Ru(H)2(PPh3)2 skeleton where the two hydrides and two phosphines are mutually cis (Scheme 4a). In this situation, the two hydrides are chemically equivalent but magnetically inequivalent because of cis and trans phosphorus couplings, which satisfies the symmetry-breaking conditions needed to detect PHIP. The 31P resonance of 4-PP was found at δ 47.8. The identities of 4-CN and 4-PP were confirmed by in situ irradiation of a C6D6 solution of 1 in the presence of a 10-fold excess of 15N-pyridine under p-H2 pressure with the pulsed laser. 1H−15N HMQC spectroscopy showed a cross peak between the hydride peak at δ −14.32 for complex 4-CN and a resonance at δ 270.4 in the 15N spectrum which now exhibits a trans 15N coupling of JNH = 12 Hz (see the Supporting Information). A cross peak was also observed between the hydride resonance for complex 4-PP and a signal in the 15N NMR spectrum at δ 256.3, indicating a small cis JNH coupling (99%. Pressures of p-H2 were measured with an MKS Baratron capacitance manometer. Deuterated solvents for use in NMR were degassed and dried before use; benzene-d6 and toluene-d8 were obtained from Aldrich and dried on potassium mirrors in ampules fitted with a greaseless tap. 15N-Pyridine (Aldrich) was used as received. NMR Measurements. Ex Situ UV Photolysis Setup. Photochemical reactions were performed with an Oriel 350 W high-pressure xenon arc lamp. Unwanted heating was minimized by use of a water filter of 10 cm length between the sample and the lamp. Continuous Wave Laser Experiments. The in situ photolysis equipment has been described before.62 In summary, in situ photolysis experiments were performed using a wide-bore Bruker DRX-400 NMR spectrometer equipped with a 63 mW Kimmon IK series He− Cd laser at 325 nm. The laser beam was directed into the sample in the spectrometer through the air gap between the magnet bore and a narrow-bore probe. The sample was cooled using a liquid N2 boil-off evaporator. The laser was mounted on a specially designed platform situated in front of the NMR spectrometer that could be adjusted both horizontally and vertically. The laser alignment was optimized by using an NMR sample of Ru(CO)3(dppe) (dppe = Ph2PCH2CH2PPh2) in deuterated toluene, pressurized with p-H2. On exposure to UV light the sample reacts with p-H2 to generate enhanced resonances arising from Ru(H)2(CO)3(dppe). Continuous recording of the spectra allowed the optimal position of the laser beam to be identified. Pulsed Laser Experiments. All NMR spectra were recorded on a Bruker Avance II 600 MHz spectrometer with a 14 T wide-bore magnet fitted with a 5 mm BBO probe. In situ laser photolysis was carried out with a pulsed Nd:YAG laser (Continuum Surelite II) fitted with a frequency-tripling crystal (output 355 nm). Operating conditions were typically as follows: 10 Hz repetition rate, flash

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CONCLUSIONS The evidence from in situ photochemistry of 1 with both NMR and IR detection that PPh3 loss competes with H2 reductive elimination is very strong indeed. When we first obtained NMR evidence for PPh3 substitution by H2 to form Ru(H)2(η2H2)(CO)(PPh3)2 (2), the experiments seemed to conflict with our earlier TRIR experiments.15 However, with the improved performance of modern TRIR experiments, it is now evident that we missed this reaction because of the need for NMR spectroscopy at low temperature and TRIR spectroscopy with greater sensitivity and time resolution. Our NMR experiments K

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Organometallics lamp voltage 1.49 kV, and Q-switch delay increased from the standard to 320 μs yielding a laser power of 75 mW in internal mode. The energy of a single laser pulse was measured using an energy meter calibrated for 355 nm to be ∼29.8 mJ under our operating conditions (external triggering with Q-switch delay set to 150 μs). The unfocused laser beam is directed at the base of the spectrometer and reflected up into the probe via a mirror as previously reported.32 Adjustment screws control the vertical and horizontal position of the mirror, which is on a kinematic mount. The system is fully shielded from the operator, and the screws of the kinematic mount can be adjusted from outside the shield. The laser radiation is incident on a fixed mirror that is level with the sample and passes through a hole in the probe onto the NMR tube. Standard NMR tubes fitted with Young taps were used. The samples contained 1−2 mg of compound (Abs355 ≈ 0.7) and approximately 0.4 mL of solvent. A sample of Ru(dppe)2H2 in C6D6 was used for laser alignment with p-H2 amplification in real time. Standard NMR pulse sequences were modified for use with p-H2 by including a synchronized laser initiation sequence prior to NMR excitation. A purpose-written program was used to control the laser firing from the NMR console with the laser set on external triggering. The program sets the laser to fire one warm-up shot before the fire signal. The NMR pulse was initiated at a set delay time (τ) following the fire signal. The intrinsic time delay between sending the fire signal from the spectrometer and the actual firing of the laser pulse was measured with a photodiode and an oscilloscope to be 150 μs (equal to the Q-switch delay for the generation of the pulse). This signal delay was incorporated into the pulse sequence such that synchronized measurements with a time delay, τ, were achieved by setting the spectrometer delay to τ + 150 μs. The precision of this delay between the laser and radio frequency (rf) pulses was controlled by the 200 ns clock of the spectrometer. TRIR Measurements. Our time-resolved infrared (TRIR) measurements were based on a pump−probe method that has been described in detail previously.30,63 In brief, the probe source is a broadband mid-IR pulse with 100 fs duration (fwhm) and around 1 μJ energy at 1 kHz. The pump source is the third harmonic output (355 nm) of a Q-switched Nd:YVO laser with 0.5 ps duration (fwhm) and around 3 μJ energy and is synchronized to the probe pulse. The delay between pump and probe pulses can be controlled with a pulse generator (DG535, Stanford Research System) from 0.5 ns to 100 μs. The broad-band transmitted probe pulse is detected with a 128element HgCdTe array detector. The sample solutions were flowed through a CaF2-windowed IR cell, path length 0.25 mm, which was rastered in two dimensions at high speed to reduce overheating and degradation of the sample solution. All spectral and kinetic fitting procedures were carried out using Microcal Origin 7 software. Low-Temperature Photolysis. The low-temperature photolysis IR experiments were performed in a manner similar to that described previously.64 The high-pressure−low-temperature (HP-LT) cell used in the low-temperature experiments has been described in detail elsewhere.65 Briefly, the HP-LT cell was filled with a solution of 1 dissolved in toluene-d8. Toluene-d8 was used to minimize IR solvent background issues and to permit low-temperature experiments in solution because of its lower freezing point in comparison to that of benzene-d6. The cell was attached to a cold finger of a cryogenic cooling system and cooled to the required temperature (220 K). The photolysis source used in these experiments was a Philips HPK 125W medium-pressure mercury arc lamp, which provided broad-band UV and visible light. IR spectra were recorded using a Nicolet 730 interferometer linked to a computer running Omnic software. IR Spectroscopy. Other IR spectra were recorded on a Mattson Unicam RS FTIR instrument, connected to a PC running WINFIRST software, or a Nicolet Nexus apparatus, connected to a PC running Omnic E.S.P. 5.2 software. UV−Vis Spectroscopy. UV−vis spectra were recorded on a Perkin-Lambda 7 spectrometer, using a PC running PECSS software. DFT Calculations. Density functional theory calculations were used to optimize geometries and simulate harmonic vibrational frequencies for several of the complexes (see the Supporting Information). Preliminary calculations of the parent species performed

with the Stuttgart relativistic small core pseudopotential and basis set mixed with the 6-311G(d) basis set for nonmetal atoms,66 and using the B3LYP,67,68 PBE0,69 and M0670 functionals, representing 20, 25, and 27% HF exchange, respectively, found that M06 gave the closest match with experiment. Consequently, the M06 level of theory within the Q-Chem quantum-chemical software package was adopted for fuller calculations.71 Calculations were converged then using the double-ζ 6-31G(d) basis set for C, N, O, P, and H atoms and the quasi-relativistic LANL2DZ pseudopotential and basis set for Ru.72 This combination has been labeled as LACVP(d). Optimized geometries were confirmed by the absence of imaginary frequencies, and these harmonic frequencies have been scaled by a uniform factor of 0.96 to account for anharmonic and experimental effects.73

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.7b00802. Experimental datasets associated with this paper were deposited with Univ. of York library. NMR spectra, pulse sequences used in laser pump-NMR probe experiments, T1(min) relaxation, TRIR difference spectra, FTIR spectra, DFT calculated structures and CO-stretching frequencies, and calculated and observed ν(CO) values for pyridine complexes (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail for S.B.D.: [email protected]. *E-mail for M.W.G.: [email protected]. *E-mail for R.N.P.: [email protected]. ORCID

Barbara Procacci: 0000-0001-7044-0560 Simon B. Duckett: 0000-0002-9788-6615 Michael W. George: 0000-0002-7844-1696 Magnus W. D. Hanson-Heine: 0000-0002-6709-297X Raphael Horvath: 0000-0002-2695-4895 Robin N. Perutz: 0000-0001-6286-0282 Khuong Q. Vuong: 0000-0001-9558-9273 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful for financial support from the EPSRC (grants EP/K022792/1 and EP/D058031). We acknowledge assistance from Dr. Pedro Aguiar. M.W.G. gratefully acknowledges receipt of a Wolfson Merit Award.

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DOI: 10.1021/acs.organomet.7b00802 Organometallics XXXX, XXX, XXX−XXX